WO2022044409A1 - リチウムイオン二次電池 - Google Patents

リチウムイオン二次電池 Download PDF

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Publication number
WO2022044409A1
WO2022044409A1 PCT/JP2021/013289 JP2021013289W WO2022044409A1 WO 2022044409 A1 WO2022044409 A1 WO 2022044409A1 JP 2021013289 W JP2021013289 W JP 2021013289W WO 2022044409 A1 WO2022044409 A1 WO 2022044409A1
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Prior art keywords
electrode layer
negative electrode
current collector
layer
positive electrode
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Ceased
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PCT/JP2021/013289
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English (en)
French (fr)
Japanese (ja)
Inventor
幸信 由良
憲吾 大石
俊介 水上
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to EP21860841.2A priority Critical patent/EP4207378A4/en
Priority to KR1020237005718A priority patent/KR102851727B1/ko
Priority to JP2022545297A priority patent/JP7620637B2/ja
Priority to CN202180050496.1A priority patent/CN115956305A/zh
Publication of WO2022044409A1 publication Critical patent/WO2022044409A1/ja
Priority to US18/171,863 priority patent/US20230198110A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery.
  • Lithium-ion secondary batteries are widely used in various devices that require charging.
  • a powder dispersion type positive electrode (so-called coated electrode) manufactured by applying and drying a positive electrode mixture containing a positive electrode active material, a conductive auxiliary agent, a binder, etc. is adopted. ing.
  • the powder-dispersed positive electrode contains a relatively large amount (for example, about 10% by weight) of components (binder and conductive auxiliary agent) that do not contribute to the capacity, and therefore, the lithium composite oxide as the positive electrode active material is used.
  • the filling density is low. Therefore, there is a lot of room for improvement in the powder dispersion type positive electrode in terms of capacity and charge / discharge efficiency. Therefore, attempts have been made to improve the capacity and charge / discharge efficiency by forming the positive electrode or the positive electrode active material layer with a lithium composite oxide sintered body plate.
  • Patent Document 1 Japanese Patent Laid-Open No. 5587052 provides a lithium ion secondary battery including a positive electrode current collector and a positive electrode active material layer bonded to the positive electrode current collector via a conductive bonding layer.
  • the positive electrode of is disclosed.
  • the positive electrode active material layer is said to be made of a lithium composite oxide sintered body plate having a thickness of 30 ⁇ m or more, a porosity of 3 to 30%, and an open pore ratio of 70% or more.
  • Patent Document 2 Patent No. 6374634 discloses a lithium composite oxide sintered body plate such as lithium cobalt oxide LiCoO 2 (hereinafter referred to as LCO) used for the positive electrode of a lithium ion secondary battery. ing.
  • LCO lithium cobalt oxide LiCoO 2
  • the open pore ratio is 70% or more
  • the thickness is 15 to 200 ⁇ m
  • the primary particle size which is the average particle size of the plurality of primary particles, is 20 ⁇ m or less.
  • the average value of the angles formed by the (003) surface of the plurality of primary particles and the plate surface of the lithium composite oxide sintered body plate, that is, the average inclination angle is 0 °. It is said that it exceeds and is 30 ° or less.
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2015-185337 discloses a lithium ion secondary battery using a lithium titanate (Li 4 Ti 5 O 12 ) sintered body for a positive electrode or a negative electrode.
  • Patent Document 4 Japanese Patent No. 63924903 discloses a sintered body plate of lithium titanate Li 4 Ti 5 O 12 (hereinafter referred to as LTO) used for a negative electrode of a lithium ion secondary battery.
  • This LTO sintered body plate has a structure in which a plurality of primary particles are bonded, has a thickness of 10 to 290 ⁇ m, and has a primary particle size of 1.2 ⁇ m, which is the average particle size of the plurality of primary particles. It is said that the porosity is 21 to 45% and the open pore ratio is 60% or more.
  • Patent Document 5 (WO2019 / 221140A1) is composed of a positive electrode layer made of a sintered body of a lithium composite oxide (for example, lithium cobalt oxide) and a titanium-containing sintered body (for example, lithium titanate).
  • a lithium ion secondary battery comprising a negative electrode layer, a ceramic separator, and an electrolyte impregnated in the ceramic separator is disclosed.
  • the positive electrode layer, the ceramic separator, and the negative electrode layer form one integrally sintered body plate as a whole, whereby the positive electrode layer, the ceramic separator, and the negative electrode layer are bonded to each other.
  • Patent Document 5 WO2019 / 221140A1
  • the yield and long-term performance were inferior.
  • the present inventors have now described an integrally sintered body including a current collecting layer in an integrally sintered body type lithium ion secondary battery in which the positive electrode layer, the ceramic separator and the negative electrode layer form one integrally sintered body as a whole.
  • the yield and long-term performance can be improved by keeping the ratio of the region where the current collector layer and the negative electrode layer in direct contact at the bonding interface within a predetermined range.
  • a positive electrode layer composed of a lithium composite oxide sintered body and A negative electrode layer composed of a titanium-containing sintered body and A ceramic separator interposed between the positive electrode layer and the negative electrode layer, At least the electrolyte impregnated in the ceramic separator and With a unit cell and
  • B A current collector layer disposed on both sides of the unit cell or a surface on the negative electrode layer side.
  • An exterior body having a closed space and accommodating the unit cell in the closed space It is a lithium-ion secondary battery equipped with
  • the positive electrode layer, the ceramic separator, the negative electrode layer, and the current collector layer form an integral sintered body as a whole, whereby the positive electrode layer, the ceramic separator, the negative electrode layer, and the current collector are formed.
  • the layers are bonded to each other When the interface between the current collector layer and the negative electrode layer is observed in cross section, the ratio of the region in which the current collector layer and the negative electrode layer are in direct contact with each other at the interface is 45 to 90%.
  • the next battery is provided.
  • FIG. 6 It is a schematic sectional drawing of an example of the lithium ion secondary battery of this invention. It is an SEM image which shows an example of the cross section perpendicular to the layer plane of the oriented positive electrode layer. It is an EBSD image in the cross section of the oriented positive electrode layer shown in FIG. 6 is a histogram showing the distribution of orientation angles of primary particles in the EBSD image of FIG. 3 on an area basis. It is a schematic cross-sectional view which conceptually shows an example of the layer structure of the laminated cell which can be adopted in the lithium ion secondary battery of this invention. It is a schematic cross-sectional view conceptually showing another example of the layer structure of the laminated cell which can be adopted in the lithium ion secondary battery of this invention.
  • FIG. 1 schematically shows an example of the lithium ion secondary battery of the present invention.
  • the lithium ion secondary battery 10 shown in FIG. 1 is in the form of a coin-type battery, but the present invention is not limited to this, and batteries of other forms may be used.
  • the lithium ion secondary battery 10 includes a unit cell 12, a current collector layer 20 arranged on both sides of the unit cell 12 or a surface on the negative electrode layer 18 side, and an exterior body 24.
  • the exterior body 24 has a closed space, and the unit cell 12 is housed in the closed space.
  • the unit cell 12 includes a positive electrode layer 14 made of a lithium composite oxide sintered body, a ceramic separator 16, a negative electrode layer 18 made of a titanium-containing sintered body, and an electrolytic solution 22.
  • the ceramic separator 16 is interposed between the positive electrode layer 14 and the negative electrode layer 18.
  • the electrolytic solution 22 is impregnated at least in the ceramic separator, and typically also in the positive electrode layer 14 and / or the negative electrode layer 18.
  • the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 form an integral sintered body as a whole, whereby the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer are formed. 20 are bonded to each other.
  • the ratio of the region where the current collector layer 20 and the negative electrode layer 18 are in direct contact with each other at the interface is 45 to 90%.
  • the integrally sintered body including the current collector layer 20 occupies the region where the current collector layer 20 and the negative electrode layer 18 are in direct contact with each other at the bonding interface.
  • interface peeling for example, peeling at the interface between the positive electrode layer and the ceramic separator, peeling at the interface between the negative electrode layer and the ceramic separator, and the interface between the positive electrode layer and the current collector layer.
  • peeling is likely to occur at the interface between the negative electrode layer and the current collector layer.
  • the sintered body type electrode layer inevitably has pores (due to the structure in which a large number of primary particles are necked), so that there are voids between the electrode layer (particularly the negative electrode layer) and other layers. It is thought that the existence of a large number has an effect.
  • the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 form one integral sintered body as a whole, resulting in a positive electrode.
  • the layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 are sufficiently bonded to each other.
  • the ratio of the region where the current collector layer 20 and the negative electrode layer 18 are in direct contact at the bonding interface within the range of 45 to 90%, sufficient contact between the negative electrode layer 18 and the current collector layer 20 is achieved. While the peeling prevention effect can be obtained, the adverse effect (long-term performance deterioration) due to the direct contact area between the negative electrode layer 18 and the current collector layer 20 being too wide can be avoided. It is not clear why the long-term performance (for example, discharge capacity retention rate) deteriorates if the direct contact area between the negative electrode layer 18 and the current collector layer 20 is too large, but the stress generated during charging and discharging is the negative electrode layer 18 and the current collector layer. It is considered that this is because it is likely to occur at the interface with 20 and the interface peeling is likely to occur.
  • the ratio of the region where the current collector layer 20 and the negative electrode layer 18 are in direct contact with each other at the interface is 45 to 90%, preferably 45. It is ⁇ 85%, more preferably 47-80%, still more preferably 50-75%, and particularly preferably 55-70%.
  • the ratio occupied by the direct contact region is 1000 times the cross section including the current collector layer 20 and the negative electrode layer 18 obtained by polishing with a cross section polisher (CP) (cross section perpendicular to the plate surface of the electrode plate).
  • CP cross section polisher
  • each region of the current collector layer (specified by the current collector layer constituent elements such as Au), the negative electrode layer (specified by the negative electrode layer constituent elements such as Ti), and the voids. Is defined.
  • the length L 1 of the line segment of the current collector layer constituting the interface (hereinafter referred to as the current collector layer interface length L 1 ) and the line segment of the interface where the current collector layer and the negative electrode layer are in direct contact with each other.
  • the total length L 2 (hereinafter referred to as the direct contact length L 2 ) is determined.
  • the positive electrode layer 14 is made of a lithium composite oxide sintered body.
  • the fact that the positive electrode layer 14 is made of a sintered body means that the positive electrode layer 14 does not contain a binder or a conductive auxiliary agent. This is because even if the green sheet contains a binder, the binder disappears or burns out during firing. Since the positive electrode layer 14 does not contain a binder, there is an advantage that deterioration of the positive electrode due to the electrolytic solution 22 can be avoided.
  • the lithium composite oxide constituting the sintered body is particularly preferably lithium cobalt oxide (typically LiCoO 2 (hereinafter, may be abbreviated as LCO)).
  • Patent Document 1 Patent No. 5587052
  • Patent Document 2 Patent No. 6374634
  • the positive electrode layer 14, that is, the lithium composite oxide sintered body plate contains a plurality of primary particles composed of the lithium composite oxide, and the plurality of primary particles are attached to the layer surface of the positive electrode layer. It is an oriented positive electrode layer oriented at an average orientation angle of more than 0 ° and 30 ° or less.
  • FIG. 2 shows an example of a cross-sectional SEM image perpendicular to the layer surface of the oriented positive electrode layer 14, while FIG. 3 shows an electron backscatter diffraction (EBSD) image in a cross section perpendicular to the layer surface of the oriented positive electrode layer 14. .
  • FIG. 2 shows an example of a cross-sectional SEM image perpendicular to the layer surface of the oriented positive electrode layer 14
  • FIG. 3 shows an electron backscatter diffraction (EBSD) image in a cross section perpendicular to the layer surface of the oriented positive electrode layer 14. .
  • FIG. 1 shows an electron backscatter diffraction
  • FIG. 4 shows a histogram showing the distribution of the orientation angles of the primary particles 11 in the EBSD image of FIG. 3 on an area basis.
  • the discontinuity of the crystal orientation can be observed.
  • the orientation angle of each primary particle 11 is shown by the shade of color, and the darker the color, the smaller the orientation angle.
  • the orientation angle is an inclination angle formed by the (003) plane of each primary particle 11 with respect to the layer plane direction.
  • the portions shown in black inside the oriented positive electrode layer 14 are pores.
  • the oriented positive electrode layer 14 is an oriented sintered body composed of a plurality of primary particles 11 bonded to each other.
  • Each primary particle 11 is mainly plate-shaped, but may include those formed in a rectangular parallelepiped shape, a cube shape, a spherical shape, or the like.
  • the cross-sectional shape of each primary particle 11 is not particularly limited, and may be a rectangle, a polygon other than a rectangle, a circle, an ellipse, or a complicated shape other than these.
  • Each primary particle 11 is composed of a lithium composite oxide.
  • the lithium composite oxide is Li x MO 2 (0.05 ⁇ x ⁇ 1.10, M is at least one transition metal, and M is typically one or more of Co, Ni and Mn. Is an oxide represented by).
  • the lithium composite oxide has a layered rock salt structure.
  • the layered rock salt structure is a crystal structure in which a lithium layer and a transition metal layer other than lithium are alternately laminated with an oxygen layer sandwiched between them, that is, a transition metal ion layer and a lithium single layer are alternately laminated via oxide ions.
  • lithium composite oxides are Li x CoO 2 (lithium cobaltate), Li x NiO 2 (lithium nickelate), Li x MnO 2 (lithium manganate), Li x NiMnO 2 (lithium nickel manganate).
  • Li x NiCoO 2 lithium nickel cobaltate
  • Li x CoNiMnO 2 cobalt, nickel, lithium manganate
  • Li x CoMnO 2 lithium cobalt manganate
  • Li x CoO 2 is particularly preferable.
  • Lithium cobaltate typically LiCoO 2 .
  • Lithium composite oxides include Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te, Ba. , Bi, and W may contain one or more elements selected from.
  • the average value of the orientation angles of each primary particle 11, that is, the average orientation angle is more than 0 ° and 30 ° or less.
  • the oriented positive electrode layer 14 is dominated by expansion and contraction in the thickness direction rather than the layer surface direction, so that the expansion and contraction of the oriented positive electrode layer 14 becomes smooth. This is because the inflow and outflow of lithium ions becomes smooth.
  • the expansion and contraction of the oriented positive electrode layer 14 due to the ingress and egress of lithium ions becomes predominant in the direction perpendicular to the layer surface, stress at the junction interface between the oriented positive electrode layer 14 and the ceramic separator 16 is less likely to occur. It facilitates the maintenance of good bonds at the interface.
  • the average orientation angle of the primary particles 11 is obtained by the following method. First, in an EBSD image in which a rectangular region of 95 ⁇ m ⁇ 125 ⁇ m is observed at a magnification of 1000 times as shown in FIG. 3, three horizontal lines that divide the oriented positive electrode layer 14 into four equal parts in the thickness direction and an oriented positive electrode layer 14 Draw three vertical lines that divide the above into four equal parts in the layer direction. Next, the average orientation angle of the primary particles 11 is obtained by arithmetically averaging the orientation angles of all the primary particles 11 intersecting at least one of the three horizontal lines and the three vertical lines. The average orientation angle of the primary particles 11 is preferably 30 ° or less, more preferably 25 ° or less, from the viewpoint of further improving the rate characteristics. The average orientation angle of the primary particles 11 is preferably 2 ° or more, more preferably 5 ° or more, from the viewpoint of further improving the rate characteristics.
  • the orientation angle of each primary particle 11 may be widely distributed from 0 ° to 90 °, but most of them are distributed in a region of more than 0 ° and 30 ° or less. Is preferable. That is, when the cross section of the oriented sintered body constituting the oriented positive electrode layer 14 is analyzed by EBSD, the orientation angle of the oriented positive electrode layer 14 with respect to the layer surface of the primary particles 11 included in the analyzed cross section exceeds 0 °.
  • the total area of the primary particles 11 (hereinafter referred to as low-angle primary particles) having a temperature of 30 ° or less is that of the primary particles 11 included in the cross section (specifically, the 30 primary particles 11 used to calculate the average orientation angle).
  • the proportion of the primary particles 11 having high mutual adhesion can be increased, so that the rate characteristics can be further improved.
  • the total area of the low-angle primary particles having an orientation angle of 20 ° or less is 50% or more of the total area of the 30 primary particles 11 used for calculating the average orientation angle. ..
  • the total area of the low-angle primary particles having an orientation angle of 10 ° or less is 15% or more with respect to the total area of the 30 primary particles 11 used for calculating the average orientation angle. ..
  • each primary particle 11 is mainly plate-shaped, the cross section of each primary particle 11 extends in a predetermined direction as shown in FIGS. 2 and 3, and is typically substantially rectangular. That is, when the cross section of the oriented sintered body is analyzed by EBSD, the total area of the primary particles 11 having an aspect ratio of 4 or more among the primary particles 11 included in the analyzed cross section is included in the cross section. It is preferably 70% or more, more preferably 80% or more, based on the total area of the particles 11 (specifically, the 30 primary particles 11 used for calculating the average orientation angle). Specifically, in the EBSD image as shown in FIG. 3, the mutual adhesion between the primary particles 11 can be further improved, and as a result, the rate characteristics can be further improved.
  • the aspect ratio of the primary particle 11 is a value obtained by dividing the maximum ferret diameter of the primary particle 11 by the minimum ferret diameter.
  • the maximum ferret diameter is the maximum distance between the straight lines when the primary particles 11 are sandwiched between two parallel straight lines on the EBSD image when the cross section is observed.
  • the minimum ferret diameter is the minimum distance between the straight lines when the primary particles 11 are sandwiched between two parallel straight lines on the EBSD image.
  • the average particle size of the plurality of primary particles constituting the oriented sintered body is 5 ⁇ m or more.
  • the average particle size of the 30 primary particles 11 used for calculating the average orientation angle is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, still more preferably 12 ⁇ m or more.
  • the average particle size of the primary particles 11 is a value obtained by arithmetically averaging the circle-equivalent diameters of each primary particle 11.
  • the circle-equivalent diameter is the diameter of a circle having the same area as each primary particle 11 on the EBSD image.
  • the positive electrode layer 14 preferably contains pores.
  • the inclusion of pores, especially open pores, in the sintered body allows the electrolyte to penetrate into the sintered body when incorporated into the battery as a positive electrode plate, resulting in improved lithium ion conductivity. be able to. This is because there are two types of conduction of lithium ions in the sintered body: conduction through the constituent particles of the sintered body and conduction through the electrolytic solution in the pores, but conduction through the electrolytic solution in the pores is better. This is because it is overwhelmingly fast.
  • the positive electrode layer 14, that is, the lithium composite oxide sintered body preferably has a porosity of 20 to 60%, more preferably 25 to 55%, still more preferably 30 to 50%, and particularly preferably 30 to 45%. be.
  • the stress release effect due to the pores and the increase in capacity can be expected, and the mutual adhesion between the primary particles 11 can be further improved, so that the rate characteristics can be further improved.
  • the porosity of the sintered body is calculated by polishing the cross section of the positive electrode layer by CP (cross section polisher) polishing and then observing the SEM at a magnification of 1000 to binarize the obtained SEM image.
  • the average circle-equivalent diameter of each pore formed inside the oriented sintered body is not particularly limited, but is preferably 8 ⁇ m or less.
  • the average circle-equivalent diameter of the pores is a value obtained by arithmetically averaging the circle-equivalent diameters of 10 pores on the EBSD image.
  • the equivalent circle diameter is the diameter of a circle having the same area as each pore on the EBSD image. It is preferable that each pore formed inside the oriented sintered body is an open pore connected to the outside of the positive electrode layer 14.
  • the positive electrode layer 14, that is, the average pore diameter of the lithium composite oxide sintered body is preferably 0.1 to 10.0 ⁇ m, more preferably 0.2 to 5.0 ⁇ m, and further preferably 0.25 to 3. It is 0 ⁇ m. Within the above range, the occurrence of stress concentration in the local area of large pores is suppressed, and the stress in the sintered body is easily released uniformly.
  • the thickness of the positive electrode layer 14 is preferably 20 to 1000 ⁇ m, more preferably 30 to 900 ⁇ m, and even more preferably 40 to 800 ⁇ m. Within such a range, the active material capacity per unit area is increased to improve the energy density of the lithium ion secondary battery 10, and the battery characteristics are deteriorated (particularly, the resistance value is increased) due to repeated charging and discharging. Can be suppressed.
  • the negative electrode layer 18 is made of a titanium-containing sintered body.
  • the titanium-containing sintered body preferably contains lithium titanate Li 4 Ti 5 O 12 (hereinafter, LTO) or niobium-titanium composite oxide Nb 2 TiO 7 , and more preferably contains LTO.
  • LTO lithium titanate Li 4 Ti 5 O 12
  • Nb 2 TiO 7 niobium-titanium composite oxide
  • LTO is typically known to have a spinel-type structure
  • other structures may be adopted during charging / discharging.
  • LTO reacts in a two-phase coexistence of Li 4 Ti 5 O 12 (spinel structure) and Li 7 Ti 5 O 12 (rock salt structure) during charging and discharging. Therefore, LTO is not limited to the spinel structure.
  • the LTO sintered body can be produced according to the methods described in Patent Document 3 (Japanese Patent Laid-Open No. 2015-185337) and Patent Document 4 (Japanese Patent Laid-Open No. 6392493).
  • the negative electrode layer 18, that is, the titanium-containing sintered body has a structure in which a plurality of (that is, a large number of) primary particles are bonded. Therefore, it is preferable that these primary particles are composed of LTO or Nb 2 TiO 7 .
  • the thickness of the negative electrode layer 18 is preferably 20 to 1000 ⁇ m, more preferably 30 to 900 ⁇ m, and even more preferably 40 to 800 ⁇ m.
  • the thickness of the negative electrode layer 18 is obtained, for example, by measuring the distance between the layer surfaces observed substantially in parallel when the cross section of the negative electrode layer 18 is observed by an SEM (scanning electron microscope).
  • the primary particle size which is the average particle size of the plurality of primary particles constituting the negative electrode layer 18, is preferably 1.2 ⁇ m or less, more preferably 0.02 to 1.2 ⁇ m, and further preferably 0.05 to 0.7 ⁇ m. .. Within such a range, both lithium ion conductivity and electron conductivity are likely to be compatible, which contributes to the improvement of rate performance.
  • the negative electrode layer 18 preferably contains pores.
  • the inclusion of pores, especially open pores, in the sintered body allows the electrolyte to penetrate into the sintered body when incorporated into the battery as the negative electrode layer, resulting in improved lithium ion conductivity. be able to. This is because there are two types of conduction of lithium ions in the sintered body: conduction through the constituent particles of the sintered body and conduction through the electrolytic solution in the pores, but conduction through the electrolytic solution in the pores is better. This is because it is overwhelmingly fast.
  • the porosity of the negative electrode layer 18 is preferably 20 to 60%, more preferably 30 to 55%, and even more preferably 35 to 50%. Within such a range, both lithium ion conductivity and electron conductivity are likely to be compatible, which contributes to the improvement of rate performance.
  • the average pore diameter of the negative electrode layer 18 is 0.08 to 5.0 ⁇ m, preferably 0.1 to 3.0 ⁇ m, and more preferably 0.12 to 1.5 ⁇ m. Within such a range, both lithium ion conductivity and electron conductivity are likely to be compatible, which contributes to the improvement of rate performance.
  • the ceramic separator 16 is a microporous ceramic film.
  • the ceramic separator 16 has not only excellent heat resistance but also an advantage that it can be manufactured as one integrally sintered body together with the positive electrode layer 14, the negative electrode layer 18 and the current collector layer 20.
  • the ceramic contained in the ceramic separator 16 is preferably at least one selected from MgO, Al 2 O 3 , ZrO 2 , SiC, Si 3 N 4 , AlN, and cordierite, and more preferably MgO, Al. At least one selected from 2O 3 and ZrO 2 .
  • the thickness of the ceramic separator 16 is preferably 3 to 40 ⁇ m, more preferably 5 to 35 ⁇ m, and even more preferably 10 to 30 ⁇ m.
  • the porosity of the ceramic separator 16 is preferably 30 to 85%, more preferably 40 to 80%.
  • the ceramic separator 16 may contain a glass component from the viewpoint of improving the adhesiveness with the positive electrode layer 14 and the negative electrode layer 18.
  • the content ratio of the glass component in the ceramic separator 16 is preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight, still more preferably 0.5, based on the total weight of the ceramic separator 16. ⁇ 30% by weight.
  • the addition of the glass component to the ceramic separator 16 is preferably performed by adding a glass frit to the raw material powder of the ceramic separator.
  • the inclusion of the glass component in the ceramic separator 16 is not particularly required as long as the desired adhesiveness between the ceramic separator 16 and the positive electrode layer 14 and the negative electrode layer 18 can be ensured.
  • the current collector layer 20 is arranged on both sides of the unit cell 12 or on the surface on the negative electrode layer 18 side.
  • the current collector layer 20 is not particularly limited as long as it is a layer containing a conductive material, but it is preferable that the current collector layer 20 contains at least one selected from the group consisting of Au, Pt, Pd, and Cu.
  • the thickness of the current collector layer 20 is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, and even more preferably 0.1 to 3 ⁇ m.
  • the current collector layer 20 is indispensable on the negative electrode layer 18 side, but the current collector layer 20 may or may not exist on the positive electrode layer 14 side. For example, when the positive electrode layer 14 is an oriented positive electrode layer, the positive electrode layer 14 itself can have a current collecting function without using the current collecting layer 20 because the electron conductivity is excellent.
  • the electrolytic solution 22 is not particularly limited, and is an organic solvent (for example, a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC), a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC), or an ethylene carbonate (EC).
  • an organic solvent for example, a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC), a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC), or an ethylene carbonate (EC).
  • a commercially available electrolytic solution for a lithium battery such as a solution in which a lithium salt (for example, LiPF 6 ) salt is dissolved in a non-aqueous solvent of a mixed solvent of ethylmethyl carbonate (EMC) may be used.
  • a lithium salt for example, LiPF 6
  • the electrolytic solution 22 preferably contains lithium borofluoride (LiBF 4 ) in a non-aqueous solvent.
  • the preferred non-aqueous solvent is at least one selected from the group consisting of ⁇ -butyrolactone (GBL), ethylene carbonate (EC) and propylene carbonate (PC), and more preferably a mixed solvent consisting of EC and GBL.
  • GBL ⁇ -butyrolactone
  • EC ethylene carbonate
  • PC propylene carbonate
  • the non-aqueous solvent contains ⁇ -butyrolactone (GBL) to raise the boiling point, resulting in a significant improvement in heat resistance.
  • GBL ⁇ -butyrolactone
  • the volume ratio of EC: GBL in the EC and / or GBL-containing non-aqueous solvent is preferably 0: 1 to 1: 1 (GBL ratio 50 to 100% by volume), more preferably 0: 1 to 0: 1. 1: 1.5 (GBL ratio 60 to 100% by volume), more preferably 0: 1 to 1: 2 (GBL ratio 66.6 to 100% by volume), particularly preferably 0: 1 to 1: 3 (GBL ratio). 75 to 100% by volume).
  • Lithium borofluoride (LiBF 4 ) dissolved in a non-aqueous solvent is an electrolyte with a high decomposition temperature, which also results in a significant improvement in heat resistance.
  • the LiBF 4 concentration in the electrolytic solution 22 is preferably 0.5 to 2 mol / L, more preferably 0.6 to 1.9 mol / L, still more preferably 0.7 to 1.7 mol / L, and particularly preferably 0.7 to 1.7 mol / L. It is 0.8 to 1.5 mol / L.
  • the electrolytic solution 22 may further contain vinylene carbonate (VC) and / or fluoroethylene carbonate (FEC) and / or vinylethylene carbonate (VEC) as additives. Both VC and FEC have excellent heat resistance. Therefore, when the electrolytic solution 22 contains such an additive, an SEI film having excellent heat resistance can be formed on the surface of the negative electrode layer 18.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • VEC vinylethylene carbonate
  • a solid electrolyte or a polymer electrolyte may be used instead of the electrolytic solution 22 (in other words, a solid electrolyte or a polymer electrolyte can be used as the electrolyte in addition to the electrolytic solution 22).
  • a solid electrolyte or a polymer electrolyte can be used as the electrolyte in addition to the electrolytic solution 22.
  • the impregnation method is not particularly limited, and examples thereof include a method of melting the electrolyte and infiltrating it into the pores of the ceramic separator 16, a method of pressing the green compact of the electrolyte against the ceramic separator 16, and the like.
  • the lithium ion secondary battery 10 may have a plurality of unit cells 12 and a plurality of current collector layers 20.
  • a cell laminate multilayer cell
  • a plurality of unit cells 12 are laminated in series or in parallel via the current collector layer 20 to form a cell laminate, which is housed in the exterior body 24.
  • the portion of the cell laminate other than the electrolyte that is, the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20
  • forms one integrally sintered body as a whole which is the yield and long-term performance.
  • the number of unit cells 12 contained in the cell laminate is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.
  • the layer structure of the cell laminate is not particularly limited as long as it has a plurality of unit cells 12 (including a positive electrode layer 14, a ceramic separator 16, a negative electrode layer 18, and an electrolyte) and a current collector layer 20.
  • a plurality of unit cells 12 may be stacked in parallel with one current collector layer 20 interposed therebetween, or may be shown in FIG.
  • a plurality of unit cells 12 may be stacked in series with one current collector layer 20 interposed therebetween.
  • FIG. 7 even in a form in which a plurality of current collector layers 20 are formed on both sides of the unit cell 12 (that is, the current collector layer 20 / unit cell 12 / current collector layer 20) are laminated.
  • two current collector layers 20 are interposed between the unit cells 12. Further, as shown in FIG. 8, a ceramic separator 16 may be further interposed between adjacent current collector layers 20. In any aspect, it is desired that the current collector layers 20 are arranged on both sides (upper surface and lower surface) of the cell laminate.
  • the cell laminated body is not limited to the flat plate laminated structure in which flat plates or layers are stacked as illustrated in FIGS. 5 to 8, and may be various laminated structures including the following examples. In addition, it is preferable that any of the configurations exemplified below is one integrally sintered body as the whole cell laminated body.
  • -Folded structure A laminated structure in which a sheet having a layer structure including a unit cell and a current collector layer is folded once or multiple times to form a multi-layered structure (large area).
  • -Wound structure A laminated structure in which a sheet having a layer structure including a unit cell and a current collector layer is wound and integrated to form a multi-layered structure (large area).
  • Multilayering (larger area) is achieved by repeating the laminated units of the current collector layer / positive electrode layer / ceramic separator layer / negative electrode layer / current collector layer in the thickness direction.
  • the exterior body 24 has a closed space, in which the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, the current collector layer 20, and the electrolytic solution 22 are housed.
  • the exterior body 24 may be appropriately selected according to the type of the lithium ion secondary battery 10.
  • the exterior body 24 typically includes a positive electrode can 24a, a negative electrode can 24b, and a gasket 24c, and the positive electrode can 24a and the positive electrode can 24a.
  • the negative electrode can 24b is crimped via the gasket 24c to form a closed space.
  • the positive electrode can 24a and the negative electrode can 24b can be made of a metal such as stainless steel, and are not particularly limited.
  • the gasket 24c can be an annular member made of an insulating resin such as polypropylene, polytetrafluoroethylene, or PFA resin, and is not particularly limited.
  • the exterior body is a resin base material, and the battery elements (that is, the positive electrode layer 14, the negative electrode layer 18, the ceramic separator 16 and the electrolytic solution 22) are present. It is preferably embedded in a resin substrate.
  • the battery element may be sandwiched between a pair of resin films, and it is preferable that the resin films are bonded to each other with an adhesive or the resin films are heat-sealed by a heating press.
  • the integrally sintered body composed of the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18 and the current collector layer 20 may be manufactured by any method, but is preferably (1). 1) A green sheet corresponding to each of the positive electrode layer 14, the ceramic separator 16 and the negative electrode layer 18 was prepared, (2) the current collecting layer 20 was formed on one side of the positive electrode green sheet and / or the negative electrode green sheet, and (3). These green sheets are laminated so that the current collecting layer 20 is on the outside to form a unit laminate (corresponding to the unit cell 12), and (4) the obtained green sheet laminate is fired. Further, a cell laminate can also be produced by repeating the above steps (1) to (3).
  • a lithium composite oxide-containing green sheet as a positive electrode green sheet can be prepared as follows. First, a raw material powder composed of a lithium composite oxide is prepared. The powder preferably contains pre-synthesized plate-like particles (eg, LiCoO 2 plate-like particles) having a composition of LiMO 2 (M is as described above). The volume-based D50 particle size of the raw material powder is preferably 0.3 to 30 ⁇ m.
  • the method for producing LiCoO 2 plate-shaped particles can be carried out as follows. First, the LiCoO 2 powder is synthesized by mixing the Co 3 O 4 raw material powder and the Li 2 CO 3 raw material powder and firing them (500 to 900 ° C.
  • LiCoO 2 particles capable of conducting lithium ions parallel to the plate surface can be obtained.
  • Such LiCoO 2 particles are plate-shaped, such as a method of growing a green sheet using LiCoO 2 powder slurry and then crushing it, a flux method, hydrothermal synthesis, single crystal growth using a melt, and a sol-gel method. It can also be obtained by a method of synthesizing crystals.
  • the obtained LiCoO 2 particles are in a state of being easily cleaved along the cleavage plane. By cleaving LiCoO 2 particles by crushing, LiCoO 2 plate-like particles can be produced.
  • the plate-shaped particles may be used alone as a raw material powder, or a mixed powder of the plate-shaped powder and another raw material powder (for example, Co 3 O 4 particles) may be used as the raw material powder.
  • another raw material powder for example, Co 3 O 4 particles
  • the volume-based D50 particle size of the Co 3 O 4 raw material powder is not particularly limited and may be, for example, 0.1 to 1.0 ⁇ m, but the LiCoO 2 template particles. It is preferable that the particle size is smaller than the volume standard D50 particle size.
  • the matrix particles can also be obtained by heat-treating the Co (OH) 2 raw material at 500 ° C. to 800 ° C. for 1 to 10 hours. Further, as the matrix particles, in addition to Co 3 O 4 , Co (OH) 2 particles may be used, or LiCo O 2 particles may be used.
  • the raw material powder is composed of 100% LiCoO 2 template particles, or when LiCoO 2 particles are used as matrix particles, a large format (for example, 90 mm ⁇ 90 mm square) and flat LiCoO 2 sintered body layer is obtained by firing. Can be done. Although the mechanism is not clear, it is expected that volume change during firing is unlikely to occur or local unevenness is unlikely to occur because synthesis to LiCoO 2 is not performed during the firing process.
  • the raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • a lithium compound other than LiMO 2 (for example, lithium carbonate) may be excessively added to the slurry by about 0.5 to 30 mol% for the purpose of promoting grain growth or compensating for volatile components during the firing step described later. It is desirable not to add a pore-forming material to the slurry. It is preferable that the slurry is stirred under reduced pressure to defoam and the viscosity is adjusted to 4000 to 10000 cP. The obtained slurry is formed into a sheet to obtain a lithium composite oxide-containing green sheet.
  • Sheet molding is preferably performed using a molding method capable of applying a shearing force to plate-shaped particles (for example, template particles) in the raw material powder.
  • the average inclination angle of the primary particles can be set to more than 0 ° and 30 ° or less with respect to the sheet surface.
  • the doctor blade method is suitable as a molding method capable of applying a shearing force to the plate-shaped particles.
  • the thickness of the lithium composite oxide-containing green sheet may be appropriately set so as to be a desired thickness as described above after firing.
  • the titanium-containing green sheet as the negative electrode green sheet may be produced by any method.
  • the LTO-containing green sheet can be produced as follows. First, a raw material powder (LTO powder) composed of lithium titanate Li 4 Ti 5 O 12 is prepared. As the raw material powder, a commercially available LTO powder may be used, or a new synthetic powder may be used. For example, a powder obtained by hydrolyzing a mixture of titanium tetraisopropoxyalcohol and isopropoxylithium may be used, or a mixture containing lithium carbonate, titania and the like may be fired.
  • the volume-based D50 particle size of the raw material powder is preferably 0.05 to 5.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m.
  • pulverization treatment for example, pot mill pulverization, bead mill pulverization, jet mill pulverization, etc.
  • the raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • a lithium compound other than LiMO 2 may be excessively added to the slurry by about 0.5 to 30 mol% for the purpose of promoting grain growth or compensating for volatile components during the firing step described later. It is desirable not to add a pore-forming material to the slurry. It is preferable that the slurry is stirred under reduced pressure to defoam and the viscosity is adjusted to 4000 to 10000 cP. The obtained slurry is formed into a sheet to obtain an LTO-containing green sheet. Sheet molding can be performed by various well-known methods, but it is preferably performed by the doctor blade method. The thickness of the LTO-containing green sheet may be appropriately set so as to be a desired thickness as described above after firing.
  • the preparation of the separator green sheet can be performed as follows. First, at least one ceramic powder selected from MgO, Al 2 O 3 , ZrO 2 , SiC, Si 3 N 4 , Al N, and cordierite is prepared. Glass frit may be added to this ceramic powder.
  • the volume-based D50 particle size of the raw material powder is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m. When the particle size of the raw material powder is large, the pores tend to be large.
  • pulverization treatment for example, pot mill pulverization, bead mill pulverization, jet mill pulverization, etc.
  • the raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry. It is desirable not to add a pore-forming material to the slurry. It is preferable that the slurry is stirred under reduced pressure to defoam and the viscosity is adjusted to 4000 to 10000 cP.
  • the obtained slurry is formed into a sheet to obtain a separator green sheet.
  • Sheet molding can be performed by various well-known methods, but it is preferably performed by the doctor blade method.
  • the thickness of the separator green sheet may be appropriately set so as to be a desired thickness as described above after firing.
  • the current collector layer is not particularly limited as long as it is a layer containing a conductive material, but a current collector layer is preferably formed by firing to form a metal layer.
  • the current collecting layer may be formed by applying a metal paste (for example, Au paste, Pt paste, Pd paste or Cu paste) to one side of the positive electrode green sheet and / or the negative electrode green sheet.
  • the metal paste may be applied by any method, but it is preferable to apply the metal paste by printing because a highly accurate and controlled thickness current collector layer can be formed with high productivity.
  • the current collector layer may be formed on one side or both sides of the green sheet laminate after the formation of the green sheet laminate.
  • the pressing may be performed by a known method and is not particularly limited, but is preferably performed by a CIP (cold isotropic pressure pressurization method).
  • the preferred press pressure is 10 to 5000 kgf / cm 2 , and more preferably 50 to 3000 kgf / cm 2 . It is preferable to punch the green sheet laminate thus crimped into a desired shape (for example, coin shape or chip shape) or size with a punching die.
  • the deviation between the positive electrode layer 14 and the negative electrode layer 18 can be eliminated.
  • the end face of the positive electrode layer 14 and the end face of the negative electrode layer 18 are aligned, so that the capacity of the battery can be maximized.
  • the obtained green sheet laminate (including the current collector layer) is placed on a setter.
  • the setter is made of ceramics, preferably zirconia or magnesia.
  • the setter is preferably embossed.
  • the green sheet placed on the setter in this way is put in the sheath.
  • the sheath is also made of ceramics, preferably alumina.
  • degreasing is desired, and then firing is performed to obtain an integrally sintered body.
  • Degreasing is preferably carried out by holding at 300 to 600 ° C. for 0.5 to 20 hours.
  • the firing is preferably carried out at 650 to 900 ° C. for 0.01 to 20 hours, more preferably at 700 to 850 ° C.
  • the rate of temperature rise during firing is preferably 50 to 1500 ° C./h, more preferably 200 to 1300 ° C./h.
  • this heating rate is preferably adopted in the heating process of 600 to 900 ° C., and more preferably adopted in the heating process of 600 to 800 ° C.
  • an integrally sintered body including the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 is obtained. If the punching process is not performed at the stage of the green sheet laminated body described above, a shift between the positive electrode layer 14 and the negative electrode layer 18 may occur in the integrally sintered body in the final form.
  • the end face of the integrally sintered body by a method such as laser processing, cutting, or polishing to minimize or eliminate the above deviation.
  • a method such as laser processing, cutting, or polishing to minimize or eliminate the above deviation.
  • LiCoO 2 will be abbreviated as “LCO” and Li 4 Ti 5 O 12 will be abbreviated as “LTO”.
  • Example 1 (1) Preparation of LCO Green Sheet (Positive Green Sheet) First, Co 3 O 4 powder (manufactured by Shodo Chemical Industry Co., Ltd.) and Li 2 CO weighed so that the molar ratio of Li / Co is 1.01. After mixing the three powders (manufactured by Honjo Chemical Co., Ltd.), the powder was held at 780 ° C. for 5 hours, and the obtained powder was crushed with a pot mill so that the volume standard D50 was 0.4 ⁇ m to form a powder consisting of LCO plate-like particles.
  • the LCO slurry was prepared by stirring the obtained mixture under reduced pressure to defoam and adjusting the viscosity to 4000 cP.
  • the viscosity was measured with an LVT type viscometer manufactured by Brookfield.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an LCO green sheet.
  • the thickness of the LCO green sheet was set so that the thickness after firing was 120 ⁇ m.
  • binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • plasticizer DOP: Di (2-ethylhexyl) phthalate, manufactured by Sekisui Chemical Co., Ltd.
  • the obtained negative electrode raw material mixture was stirred under reduced pressure to defoam, and the viscosity was adjusted to 4000 cP to prepare an LTO slurry.
  • the viscosity was measured with an LVT type viscometer manufactured by Brookfield.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an LTO green sheet.
  • the thickness of the LTO green sheet was set so that the thickness after firing was 140 ⁇ m.
  • MgO Green Sheet (Separator Green Sheet) Magnesium carbonate powder (manufactured by Konoshima Chemical Co., Ltd.) was heat-treated at 900 ° C. for 5 hours to obtain MgO powder. The obtained MgO powder and glass frit (manufactured by Nippon Frit Co., Ltd., CK0199) were mixed at a weight ratio of 4: 1.
  • the obtained raw material mixture was stirred under reduced pressure to defoam, and the viscosity was adjusted to 4000 cP to prepare a slurry.
  • the viscosity was measured with an LVT type viscometer manufactured by Brookfield.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form a separator green sheet.
  • the thickness of the separator green sheet was set so that the thickness after firing was 15 ⁇ m.
  • LCO green sheet positive electrode green sheet
  • MgO green sheet separatator green sheet
  • LTO green sheet negative electrode green sheet
  • the laminate was pressed at 200 kgf / cm 2 by CIP (cold isotropic pressure pressurization method) to crimp the green sheets to each other.
  • the laminated body crimped in this way was punched into a disk shape having a diameter of 10 mm with a punching die.
  • the obtained disc-shaped laminate was degreased at 600 ° C. for 5 hours, then fired at 1000 ° C./h to 800 ° C. and held for 10 minutes, and then cooled.
  • a coin-shaped lithium ion secondary battery 10 as schematically shown in FIG. 1 was manufactured as follows. Between the positive electrode can and the negative electrode can that form the battery case, from the positive electrode can to the negative electrode can, the positive electrode current collector layer, the integrally sintered body plate (LCO positive electrode layer, MgO separator and LTO negative electrode layer), Further, the negative electrode current collector layers were housed so as to be laminated in this order, filled with an electrolytic solution, and then sealed by caulking the positive electrode can and the negative electrode can through a gasket. In this way, a coin cell type lithium ion secondary battery 10 having a diameter of 20 mm and a thickness of 3.2 mm was produced.
  • LiBF 4 was dissolved in an organic solvent in which ethylene carbonate (EC) and ⁇ -butyrolactone (GBL) were mixed at a volume ratio of 1: 3 so as to have a concentration of 1.5 mol / L.
  • EC ethylene carbonate
  • GBL ⁇ -butyrolactone
  • ⁇ Average orientation angle of primary particles> The LCO sintered body layer was polished with a cross section polisher (CP) (IB-15000CP, manufactured by JEOL Ltd.), and the obtained positive electrode layer cross section (cross section perpendicular to the layer surface of the positive electrode layer) was 1000 times as wide as the field view (125 ⁇ m). EBSD was measured at ⁇ 125 ⁇ m) to obtain an EBSD image. This EBSD measurement was performed using a Schottky field emission scanning electron microscope (manufactured by JEOL Ltd., model JSM-7800F).
  • the angle formed by the (003) plane of the primary particles and the layer plane of the positive electrode layer (that is, the inclination of the crystal orientation from (003)) is obtained as the tilt angle, and the angles thereof are obtained.
  • the average value of the angles was taken as the average orientation angle of the primary particles.
  • the average orientation angle of the primary particles in the positive electrode layer was 16 °.
  • the LCO and LTO sintered body layers and the MgO separator are polished by a cross section polisher (CP) (IB-15000CP, manufactured by JEOL Ltd.), and the obtained cross section is observed by SEM (JSM6390LA, manufactured by JEOL Ltd.) to obtain a positive electrode layer.
  • CP cross section polisher
  • SEM JSM6390LA, manufactured by JEOL Ltd.
  • ⁇ Porosity> The LCO or LTO sintered body layer and the MgO separator are polished with a cross section polisher (CP) (IB-15000CP, manufactured by JEOL Ltd.), and the cross section of the obtained positive electrode layer or negative electrode layer is 1000 times the field view (125 ⁇ m ⁇ ). SEM observation (manufactured by JEOL Ltd., JSM6390LA) was performed at 125 ⁇ m). The obtained SEM image was image-analyzed, the area of all pores was divided by the area of the positive electrode or the negative electrode, and the obtained value was multiplied by 100 to calculate the porosity (%). As a result, the porosity of the positive electrode layer was 45%, the porosity of the negative electrode layer was 45%, and the porosity of the ceramic separator was 50%.
  • CP cross section polisher
  • ⁇ Average pore diameter> The average pore diameter of the LCO or LTO sintered body layer was measured by a mercury intrusion method using a mercury porosimeter (manufactured by Shimadzu Corporation, Autopore IV9510). As a result, the average pore diameter of the positive electrode layer was 0.8 ⁇ m, the average pore diameter of the negative electrode layer was 0.5 ⁇ m, and the average pore diameter of the ceramic separator was 0.2 ⁇ m.
  • the integrally sintered body is polished with a cross section polisher (CP) (IB-15000CP, manufactured by JEOL Ltd.) to form a polished cross section (cross section perpendicular to the plate surface of the electrode plate) including the current collector layer and the negative electrode layer. did.
  • This polished cross section was observed by SEM (JSM-IT500LA, manufactured by JEOL Ltd.) and EDX measurement in a field of view (125 ⁇ m ⁇ 125 ⁇ m) 1000 times.
  • each region of the current collector layer (Au), the electrode layer (Ti) and the void is defined, and the length of the line segment of the current collector layer (Au) constituting the interface.
  • L 1 hereinafter referred to as collector layer interface length L 1
  • total length L 2 of line segments at the interface where the current collector layer (Au) and the negative electrode layer (Ti) are in direct contact hereinafter referred to as direct contact.
  • Length L 2 was determined.
  • the direct contact length L 2 is the total length of each direct contact line segment (for example, L 21 + L 22 + ... + L 2n (n is an integer)).
  • Is equal to the value obtained by subtracting the total length L3 of the line segments at the interface where.
  • Yield evaluation was carried out by performing visual inspection and battery inspection on the manufactured battery. Twenty battery samples were evaluated in each test, and if both tests were good at a rate of 80% or more, it was judged to be acceptable. The results were as shown in Table 1.
  • Example 2 A battery is manufactured in the same manner as in Example 1 except that the stacking, crimping, and firing steps of (5) above are performed as follows to form a cell laminate (laminated cell) containing three unit cells. And evaluation was performed. The results were as shown in Table 1.
  • LCO green sheet positive electrode green sheet
  • MgO green sheet separator green sheet
  • LTO green sheet negative electrode green sheet
  • Example 3 Batteries were manufactured and evaluated in the same manner as in Example 1 except that the winding, crimping, and firing steps of (5) were performed as follows to form a wound cell. The results were as shown in Table 1.
  • LCO green sheet positive electrode green sheet
  • MgO green sheet separatator green sheet
  • LTO green sheet negative electrode green sheet
  • a laminate was obtained.
  • Three of these unit laminates were produced. These laminated bodies were stacked and pressed at 200 kgf / cm 2 by CIP (cold isotropic pressure pressurization method) to crimp the green sheets to each other. The laminated body crimped in this way was heated at 90 ° C. on a hot plate and then wound with a winding machine so as to have an outer diameter of 10 mm and a thickness of 2.0 mm to obtain a laminated body.
  • the wound laminate was degreased at 600 ° C. for 5 hours, then fired at 1000 ° C./h to 800 ° C. and held for 10 minutes, and then cooled.
  • one integrally sintered body composed of a positive electrode layer (LCO sintered body layer), a ceramic separator (MgO separator), a negative electrode layer (LTO sintered body layer), and a current collector layer (Au layer) was obtained.
  • Example 4 The battery was prepared in the same manner as in Example 1 except that the LTO green sheet (negative electrode green sheet) of the above (2) was prepared as follows and the maximum temperature in the firing of the above (5) was set to 900 ° C. It was made and evaluated. The results were as shown in Table 1.
  • LTO Green Sheet (Negative Electrode Green Sheet)
  • LTO powder volume standard D50 particle size 0.06 ⁇ m, manufactured by Sigma-Aldrich Japan GK
  • raw material powder volume standard D50 particle size 0.06 ⁇ m, manufactured by Sigma-Aldrich Japan GK
  • a part of this raw material powder was heat-treated at 900 ° C. for 5 hours, and then crushed with a pot mill so as to have a D50: 2.0 ⁇ m to prepare powder A.
  • the powder A and the raw material powder were weighed and mixed so as to have a weight ratio of 50:50 to obtain an LTO mixed powder.
  • binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Industry Co., Ltd.
  • plasticizer plasticizer
  • the obtained negative electrode raw material mixture was stirred under reduced pressure to defoam, and the viscosity was adjusted to 4000 cP to prepare an LTO slurry.
  • the viscosity was measured with an LVT type viscometer manufactured by Brookfield.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an LTO green sheet.
  • the thickness of the LTO green sheet was set so that the thickness after firing was 140 ⁇ m.
  • Example 5 In the preparation of the LTO green sheet (negative electrode green sheet) of the above (2'), the mixing ratio (weight ratio) of the powder A and the raw material powder was set to 80:20, and the maximum temperature in the firing of the above (5) was 800 ° C. The batteries were prepared and evaluated in the same manner as in Example 4. The results were as shown in Table 1.
  • Example 6 In the preparation of the LTO green sheet (negative electrode green sheet) of (2') above, the mixing ratio (weight ratio) of the powder A and the raw material powder was 90:10, and the amount of the binder (polyvinyl butyral) added was 16 parts by weight. Batteries were prepared and evaluated in the same manner as in Example 4 except that the maximum temperature reached in the firing of (5) above was set to 750 ° C. The results were as shown in Table 1.
  • Example 7 In the preparation of the LTO green sheet (negative electrode green sheet) of (2') above, the mixing ratio (weight ratio) of the powder A and the raw material powder was 25:75, and the amount of the binder (polyvinyl butyral) added was 16 parts by weight. Batteries were prepared and evaluated in the same manner as in Example 4 except that the maximum temperature in the firing of (5) above was set to 1000 ° C. The results were as shown in Table 1.

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CN202180050496.1A CN115956305A (zh) 2020-08-26 2021-03-29 锂离子二次电池
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WO2024203868A1 (ja) * 2023-03-31 2024-10-03 日本碍子株式会社 リチウムイオン電池のための電極およびリチウムイオン電池

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WO2024203868A1 (ja) * 2023-03-31 2024-10-03 日本碍子株式会社 リチウムイオン電池のための電極およびリチウムイオン電池

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EP4207378A4 (en) 2025-05-21
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JP7620637B2 (ja) 2025-01-23
US20230198110A1 (en) 2023-06-22
EP4207378A1 (en) 2023-07-05
CN115956305A (zh) 2023-04-11
KR102851727B1 (ko) 2025-08-27
TW202220267A (zh) 2022-05-16

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